EP0360901A1 - Procédé et dispositif d'échantillonnage et d'analyse d'hydrocarbures - Google Patents

Procédé et dispositif d'échantillonnage et d'analyse d'hydrocarbures Download PDF

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Publication number
EP0360901A1
EP0360901A1 EP88116048A EP88116048A EP0360901A1 EP 0360901 A1 EP0360901 A1 EP 0360901A1 EP 88116048 A EP88116048 A EP 88116048A EP 88116048 A EP88116048 A EP 88116048A EP 0360901 A1 EP0360901 A1 EP 0360901A1
Authority
EP
European Patent Office
Prior art keywords
sorbent
samples
analysis
film
hydrocarbons
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP88116048A
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German (de)
English (en)
Inventor
Günter Dr. Voss
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Balzers und Leybold Deutschland Holding AG
Original Assignee
Leybold AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Leybold AG filed Critical Leybold AG
Priority to EP88116048A priority Critical patent/EP0360901A1/fr
Priority to JP1252490A priority patent/JPH02122237A/ja
Priority to US07/414,538 priority patent/US4986110A/en
Publication of EP0360901A1 publication Critical patent/EP0360901A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/02—Details
    • H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
    • H01J49/0468—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components with means for heating or cooling the sample
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/02—Devices for withdrawing samples
    • G01N1/22—Devices for withdrawing samples in the gaseous state
    • G01N1/2202—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling
    • G01N1/2214—Devices for withdrawing samples in the gaseous state involving separation of sample components during sampling by sorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/40—Concentrating samples
    • G01N1/405—Concentrating samples by adsorption or absorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N1/00—Sampling; Preparing specimens for investigation
    • G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
    • G01N1/2813—Producing thin layers of samples on a substrate, e.g. smearing, spinning-on
    • G01N2001/2826—Collecting by adsorption or absorption
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/08—Preparation using an enricher
    • G01N2030/085—Preparation using an enricher using absorbing precolumn
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
    • G01N21/55—Specular reflectivity
    • G01N21/552—Attenuated total reflection
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N30/00—Investigating or analysing materials by separation into components using adsorption, absorption or similar phenomena or using ion-exchange, e.g. chromatography or field flow fractionation
    • G01N30/02—Column chromatography
    • G01N30/04—Preparation or injection of sample to be analysed
    • G01N30/06—Preparation
    • G01N30/12—Preparation by evaporation

Definitions

  • the invention relates to a method for sampling and analyzing fluid hydrocarbons, in which the sample is collected by sorption, transported to an analysis device and analyzed.
  • the invention also relates to means suitable for carrying out this method.
  • the object of the present invention is to simplify sampling in a method of the type mentioned at the beginning and to improve it in such a way that sufficiently high sample concentrations are immediately available to the subsequent analysis step, so that concentration measures are no longer necessary.
  • this object is achieved in that the samples are collected by absorption in a solid sorbent with a relatively high solubility and with a relatively small diffusion quotient for the samples.
  • a solid sorbent with a relatively high solubility and with a relatively small diffusion quotient for the samples.
  • the small diffusion coefficient ensures that the sorbent can fulfill a storage function, i. H. can simultaneously serve as a "sampling vessel" and as a means of transport to the analysis device.
  • the hydrocarbons to be examined are usually gaseous. However, the invention can also be used with liquid samples.
  • Suitable sorbents are substances whose solubility L [cm3 / cm3 bar] is so high that the amount of sample dissolved is sufficient for identification at reasonable sorbent volumes.
  • the diffusion coefficient D [cm2 / s] must be so small that the relatively large amount of sample dissolved in the sorbent after sampling is still sufficient for identification even after it has been transported from the exposure site to the analyzer. It is particularly advantageous if the diffusion coefficient of the sorbent is extremely small.
  • Polymers such as polytetrafluoroethylene-CO-hexafluoropropylene (FEP) have proven to be particularly suitable for the sampling according to the invention.
  • Polymers of this type are available as films in various thicknesses.
  • FEP has very high solubilities for hydrocarbons (up to percent of the film mass); the diffusion coefficients are extremely small.
  • the hydrocarbon components can be so strongly enriched and stored even in films with a thickness of 0.1 mm that the stored amount is sufficient for the mass analysis.
  • FEP also has the advantage that it is chemically inert and can be produced with a uniform structure (for reproducible measurements).
  • the use of foils with a thickness of 0.1 to 1 mm has proven to be advantageous.
  • Figure 1 shows the edge of a sorbent 1, z. B. a polymer film, which is exposed for the purpose of sampling an environment to be examined (z. B. river water, landfill, food, air or the like).
  • the area contains, for example, two hydrocarbon gases G1 and G2 with the concentrations CG1 and CG2.
  • the surrounding gas components enter the polymer by solution diffusion, with the hydrocarbons - in particular the halogenated hydrocarbons - being preferred. After a certain time, depending on the solubility and diffusion coefficient, a certain amount of the hydrocarbon gases in the sorbent 1 is dissolved.
  • the concentration curve is shown over the thickness d of the film 1 (curves KG1 and KG2).
  • the surface or the edge of the sorbent 1 is identical to the y-axis of the coordinate system shown.
  • the sorbent 1 is transported from the exposure site to the analysis site.
  • the dissolved in sorbent 1 gases G1 and G2 can, for. B. be expelled thermally in a vacuum.
  • a mass analysis is carried out.
  • Figure 2 shows the associated mass spectrum with the lines of the gases G1 and G2.
  • the storage time can also by cooling the sorbent, for. B. during the time of transport from the exposure site to the analysis site, almost any length.
  • the exposure time can be extended until the gases dissolved in sorbent 1 become saturated. This state is shown by dashed lines 2 and 3 in Figure 1. This would have the advantage that the amounts of gas dissolved in sorbent 1 are very large; it would then no longer be possible to make a statement about the history of the exposure time, as will be explained with the aid of the other figures.
  • FIG. 3 shows again greatly enlarged the edge of a sorbent 1.
  • K1 is, for example, a concentration curve that arises when the hydrocarbon gas G with the concentration C G was present at the exposure site during the entire exposure period.
  • the curve K 1 corresponds to the concentration curve curves KG 1 and G 2 according to FIG. 1.
  • a quantitative statement about the concentration C G is possible if the mass spectrometer used for the evaluation is set to the mass of the gas G and this line is registered over the entire baking time becomes.
  • the result is shown (curve M1).
  • An arrow indicates the time at which the bakeout begins. Only after a few seconds, when the sorbent or the film 1 has reached a sufficiently high temperature (e.g. 200 ° Celsius), does the accelerated thermal desorption begin.
  • a sufficiently high temperature e.g. 200 ° Celsius
  • the heating process is continued until the gas G is completely desorbed.
  • the integral over the curve M1 describes the total amount of gas absorbed, which - with knowledge of D, d, L and the exposure time - is a measure of the concentration of gas G at the exposure site.
  • the curve K2 in Figure 3 shows the concentration curve for the case that the gas G was only temporarily present in the area of the exposure site.
  • the concentration of this gas G decreased to zero during the exposure period.
  • an evaluation curve M2 corresponding to the concentration curve K2 is shown. Compared to the curve M1, the curve M2 is shifted towards longer times. The points in time for the beginning and end of the presence of the gas G can be reconstructed from the special course of time and again knowing the values for D, d, L and for the exposure time.
  • FIGS. 5 and 6 additionally show the case in which a gas G was present in two different time periods during the exposure time of the film 1.
  • FIG. 5 shows a concentration curve for this case.
  • FIG. 6 shows the course of the curve which is obtained by thermal heating and mass analysis carried out at the same time. The times in which the gas G was present at the exposure location can be reconstructed from the course of the curve M.
  • FIG. 7 shows a device for carrying out the mass analysis with simultaneous heating of the film 1.
  • the film 1 is wound on a cylindrical hollow body 4, which consists of relatively coarse-pored sintered material. With a clip, not shown, the film 1 is held in the position shown.
  • the sintered hollow body is equipped with a heatable base 5, which in turn is attached to the flange 6.
  • the flange 6 serves to seal a recipient 7, which is only shown in broken lines and which can be evacuated with the aid of the vacuum pump 8.
  • the power source supplying the heater is shown as block 9.
  • a temperature sensor 11 is provided on the sintered body 4 and supplies its signals to the controller 12. With the help of this controller 12, the desired temperature profile can be set.
  • the mass spectrometer 13 is connected to the recipient 7. 14 denotes devices for evaluating the signals supplied by the mass spectrometer 13.
  • FEP has an almost constant transmission capacity of over 90% between 200 nm and 8 ⁇ m. This makes it possible to use spectroscopic methods.
  • the vibrations of the hydrocarbons collected can be found within the window mentioned.
  • the difference in transmittance up to 100% is due to reflection losses (refractive index 1.35), so that it is possible to measure very long samples.
  • the samples to be examined can, as shown in FIG. H. are brought into the beam path like a light guide.
  • Suitable coupling and decoupling systems must be arranged in front of and behind the film 1, the thickness of which can be 0.1 to 1 mm and the length of which can be approximately 200 mm. All known methods are available for the spectroscopic detection itself.
  • the method according to the invention allows the integral determination of pollutant concentrations in the air and the monitoring of water. It is possible to control the total exposure of people who work in hazardous areas. Detection of the smallest amounts of fluorine, chlorine or hydrocarbons Perchloretylene (e.g. in food) is possible. Thanks to the enrichment mechanisms, the measurements can be carried out with high sensitivity. Sampling by solution diffusion can be evaluated easily and conveniently in the laboratory.

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  • Analytical Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Immunology (AREA)
  • Pathology (AREA)
  • Engineering & Computer Science (AREA)
  • Biomedical Technology (AREA)
  • Molecular Biology (AREA)
  • Sampling And Sample Adjustment (AREA)
EP88116048A 1988-09-29 1988-09-29 Procédé et dispositif d'échantillonnage et d'analyse d'hydrocarbures Withdrawn EP0360901A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP88116048A EP0360901A1 (fr) 1988-09-29 1988-09-29 Procédé et dispositif d'échantillonnage et d'analyse d'hydrocarbures
JP1252490A JPH02122237A (ja) 1988-09-29 1989-09-29 流体炭化水素を試料採取及び分析する方法及び装置
US07/414,538 US4986110A (en) 1988-09-29 1989-09-29 Method and apparatus for taking samples of and for analyzing hydrocarbons

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP88116048A EP0360901A1 (fr) 1988-09-29 1988-09-29 Procédé et dispositif d'échantillonnage et d'analyse d'hydrocarbures

Publications (1)

Publication Number Publication Date
EP0360901A1 true EP0360901A1 (fr) 1990-04-04

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ID=8199386

Family Applications (1)

Application Number Title Priority Date Filing Date
EP88116048A Withdrawn EP0360901A1 (fr) 1988-09-29 1988-09-29 Procédé et dispositif d'échantillonnage et d'analyse d'hydrocarbures

Country Status (3)

Country Link
US (1) US4986110A (fr)
EP (1) EP0360901A1 (fr)
JP (1) JPH02122237A (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0500938A1 (fr) * 1990-08-06 1992-09-02 Institut Neorganicheskoi Khimii Sibirskogo Otdelenia Rossiiskoi Akademii Nauk Procede et dispositif de preparation de melange de vapeur-gaz standard de substance a analyser
FR2695208A1 (fr) * 1992-08-25 1994-03-04 Inocosm Laboratoires Procédé de prélèvement et de concentration de produits volatils, issus de la peroxydation des acides gras poly-insaturés, ainsi que dispositifs permettant la mise en Óoeuvre de ce procédé.
EP2098851A1 (fr) * 2008-03-07 2009-09-09 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Analyseur de gaz de désorption thermique et procédé pour l'analyse d'un environnement gazeux

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4303860C2 (de) * 1993-02-10 1995-11-09 Draegerwerk Ag Träger für den kolorimetrischen Gasnachweis in Folienverbundbauweise
RU2012111667A (ru) * 2009-08-27 2013-10-10 1ст ДИТЕКТ КОРПОРЕЙШН Предварительное концентрирование образца

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2008423A (en) * 1977-11-05 1979-06-06 British Petroleum Co Filter and method for determining proteins in water
FR2496263A1 (fr) * 1980-12-15 1982-06-18 Cogema Procede et dispositif d'echantillonnage des gaz presents dans une masse de fluide
US4541268A (en) * 1981-09-23 1985-09-17 Bruker-Franzen Analytik Gmbh Method and device for the sampling of trace elements in gases, liquids, solids or in surface layers

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL7513573A (nl) * 1975-11-20 1977-05-24 Total Raffinaderij Nederland N Werkwijze voor het verwijderen van condensaten uit gasstromen.
US4865996A (en) * 1986-07-28 1989-09-12 Brunswick Corporation Sorption/desorption method and apparatus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2008423A (en) * 1977-11-05 1979-06-06 British Petroleum Co Filter and method for determining proteins in water
FR2496263A1 (fr) * 1980-12-15 1982-06-18 Cogema Procede et dispositif d'echantillonnage des gaz presents dans une masse de fluide
US4541268A (en) * 1981-09-23 1985-09-17 Bruker-Franzen Analytik Gmbh Method and device for the sampling of trace elements in gases, liquids, solids or in surface layers

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
N.T.I.S. TECHNICAL NOTES, Nr. 9, September 1985, 'Request 100202', Teil J., Springfield, Virginia, US; "Novel methane gas sensor invented" *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0500938A1 (fr) * 1990-08-06 1992-09-02 Institut Neorganicheskoi Khimii Sibirskogo Otdelenia Rossiiskoi Akademii Nauk Procede et dispositif de preparation de melange de vapeur-gaz standard de substance a analyser
EP0500938A4 (en) * 1990-08-06 1993-01-27 Institut Neorganicheskoi Khimii Sibirskogo Otdeleniaakademii Nauk Sssr Method and service for preparation of standard vapour-gas mixture of substance to be analyzed
FR2695208A1 (fr) * 1992-08-25 1994-03-04 Inocosm Laboratoires Procédé de prélèvement et de concentration de produits volatils, issus de la peroxydation des acides gras poly-insaturés, ainsi que dispositifs permettant la mise en Óoeuvre de ce procédé.
EP2098851A1 (fr) * 2008-03-07 2009-09-09 Nederlandse Organisatie voor toegepast- natuurwetenschappelijk onderzoek TNO Analyseur de gaz de désorption thermique et procédé pour l'analyse d'un environnement gazeux
WO2009110800A1 (fr) * 2008-03-07 2009-09-11 Nederlandse Organisatie Voor Toegepast-Natuurwetenschappelijk Onderzoek Tno Analyseur de gaz de désorption thermique et procédé d'analyse d'un environnement gazeux

Also Published As

Publication number Publication date
US4986110A (en) 1991-01-22
JPH02122237A (ja) 1990-05-09

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